This invention relates to polymer compositions derived from norbornene and functional norbornene comonomers and process to prepare such polymer compositions.
Cycloolefin polymers (e.g., norbornene-based polymers) and copolymers have received a great deal of attention in recent years. They have found application in dielectric, optical, and photolithographic applications. In addition, the utility of these materials as engineering thermoplastics has been explored. As such, new cyclic olefin copolymers and catalysts for the efficient preparation of cyclic olefin polymers are constantly being sought. 
The addition polymer of norbornene (i.e., polynorbornene or poly(bicyclo[2.2.1]hept-2-ene) was originally described in U.S. Pat. No. 2,721,189. In this patent, 2 types of norbornene polymers were prepared. The first polymer was prepared by the addition polymerization of norbornene giving a fully saturated cyclic olefin polymer.
The second polymer was formed by xe2x80x9cRing Opening Metathesis Polymerizationxe2x80x9d (ROMP) giving an unsaturated polymer backbone. 
Conventional xe2x80x9cZiegler-Nattaxe2x80x9d transition metal catalysts, such as those based on titanium compounds (e.g. TiCl3 or TiCl4) in combination with organoaluminum cocatalysts, have been used to prepare the addition polymer of norbornene (see U.S. Pat. No. 3,330,815). These so-called xe2x80x9cZiegler-Nattaxe2x80x9d catalysts are quite sensitive to oxygen and are generally ineffective for the copolymerization of nonpolar and polar monomers. Following the early discovery of Zielger-Nata catalysts, there has been intense interest in the development and study of homogeneous early transition metal (Group 4-6) catalysts (xe2x80x9cmetallocene catalystsxe2x80x9d) for the polymerization of olefins. Addition polymers of norbornene have been prepared using such metallocene catalysts as shown in Kaminsky et. al. J. Mol. Cat. 1992, 72, 109; Kaminsky et. al. Makromol. Chem, Macromol. Symp. 1991, 47, 83.
More recently, others have described the use of Group 8-10 catalysts for the polymerization of norbornene and substituted norbornene. See, for example, WO 95 140448; WO 98 56839; WO 98 56837; U.S. Pat. No. 5,571,881; U.S. Pat. No. 5,468,819; and U.S. Pat. No. 5,569,730.
Recent advances in Group 8-10 catalysts for the polymerization of olefins include the following.
European Patent Application No. 381,495 describes the polymerization of olefins using palladium and nickel catalysts, which contain selected bidentate phosphorous containing ligands.
U.S. Pat. Nos. 4,906,754, 4,716,205, 5,030,606, and 5,175,326, describes the conversion of ethylene to polyethylene using anionic phosphorous, oxygen donors ligated to Ni(II). The polymerization reactions were run between 25 and 100xc2x0 C. with modest yields, producing linear polyethylene having a weight-average molecular weight ranging between 8 K and 350 K. In addition, Klabunde describes the preparation of copolymers of ethylene and functional group containing monomers.
M. Peuckert et al., Organomet. 1983, 2(5), 594, disclose the oligomerization of ethylene using phosphine/carboxylate donors ligated to Ni(II), which showed modest catalytic activity (0.14 to 1.83 TO/s). The oligomerizations were carried out at 60 to 95xc2x0 C. and 10 to 80 bar ethylene in toluene, to produce xcex1-olefins.
U.S. Pat. Nos. 4,689,437 and 4,716,138, describe the oligomerization of ethylene using phosphine, sulfonate donors ligated to Ni(II). These complexes show catalyst activities approximately 15 times greater than those reported with, phosphine, carboxylate analogs.
W. Keim et al., Angew. Chem. Int. Ed. Eng., 1981, 20, 116, and V. M. Mohring et al., Angew. Chem. Int. Ed. Eng., 1985, 24, 1001, disclose the polymerization of ethylene and the oligomerization of xcex1-olefins with aminobis(imino)phosphorane nickel catalysts.
G. Wilke, Angew. Chem. Int. Ed. Engl., 1988, 27, 185, describes a nickel allyl phosphine complex for the polymerization of ethylene.
K. A. O. Starzewski et al., Angew. Chem. Int. Ed. Engl., 1987, 26, 63, and U.S. Pat. No. 4,691,036, describe a series of bis(ylide) nickel complexes, used to polymerize ethylene to provide high molecular weight linear polyethylene.
L. K. Johnson et al., WO 96/23010; U.S. Pat. Nos. 5,866,663; 5,886,224; 5,891,963; 5,880,323; and 5,880,241; disclose the polymerization of olefins using cationic nickel, palladium, iron, and cobalt complexes containing diimine and bisoxazoline ligands. These documents also describe the polymerization of ethylene, acyclic olefins, and/or selected cyclic olefins and optionally selected unsaturated acids or esters such as acrylic acid or alkyl acrylates to provide olefin homopolymers or copolymers.
L. K Johnson et al., J. Am. Chem. Soc., 1995, 117, 6414, describe the polymerization of olefins such as ethylene, propylene, and 1 -hexene using cationic xcex1-diimine-based nickel and palladium complexes. These catalysts have been described to polymerize ethylene to high molecular weight branched polyethylene. In addition to ethylene, Pd complexes act as catalysts for the polymerization and copolymerization of olefins and methyl acrylate.
WO 97102298 discloses the polymerization of olefins using a variety of neutral N, O, P, or S donor ligands, in combination with a nickel(0) compound and an acid.
Further examples of Group 8-10 transition metal catalysts for the polymerization of olefins are illustrated in WO 98/40374, WO 98/37110, WO 98/47933, and WO 98/40420. Also described are several new polymer compositions derived from epoxybutene and derivatives thereof.
Brown et al., WO 97/17380, WO 97/48777, WO 97148739, and WO 97/48740, describe, the use of Pd xcex1-diimine catalysts for the polymerization of olefins including ethylene in the presence of air and water.
Fink et al., U.S. Pat. No. 4,724,273, describe the polymerization of xcex1-olefins using aminobis(imino)phosphorane nickel catalysts and the compositions of the resulting poly(xcex1-olefins).
Recently, Vaughan et al., WO 97/48736, Denton et al., WO 97/48742, and Sugimura et al., WO 97/38024, describe the polymerization of ethylene using silica supported xcex1-diimine nickel catalysts.
EP 884,331, discloses the use of nickel xcex1-diimine catalysts for the polymerization of ethylene in their slurry loop process.
Neutral nickel catalysts for the polymerization of olefins are set forth in WO 98/30610, WO 98/30609, WO 98/42665, and WO 98142664.
Iron and cobalt catalysts ligated by pyridine bis(imines) for the polymerization and oligomerization of ethylene are described in WO 99/02472, WO 98/27124, and WO 99112981.
Canich et al., WO 97/48735, and Mecking, DE 19707236 A1, describe the use of mixed a-diimine catalysts with group IV transition metal catalysts for the polymerization of olefins. Additional recent developments are described by Sugimura et al. in JP 96-84344 and JP 96-84343, by Yorisue et al. in JP 96-70332, by McLain et al. in WO 98/03559, by Weinberg et al. in WO 98/03521, by Wang et al. in WO 99109078, by Coughlin in WO 99110391, and by Matsunaga et al. in WO 97148737.
Notwithstanding these advances in catalysis, there remains a need for new transition metal catalysts, particularly those which are more thermally stable, allow for new polymer microstructures, or are more functional group tolerant. In addition, there is a need for novel methods of polymerizing olefins employing such catalysts, and for the novel polymers, which result.
The present invention is directed to copolymers of norbornene and functional group containing norbornene comonomers and processes for the preparation thereof. These polymers may be random, alternating or block copolymers or terpolymers, etc. In general, the present invention describes a polymer composition comprising repeat units of the formula:
[A]Sxe2x80x94 and xe2x80x94[B]T
wherein A is monomer repeat unit derived from one or more norbornene or substituted norbornene monomers of the formula: 
and B is a monomer repeat unit derived from one or more functional norbornene monomers as set forth herein. The polymers of the invention are useful in the preparation of films, fibers, and molded articles, particularly photoresists applications.
The present invention provides a polymer composition comprising repeat units of the formula:
[A]Sxe2x80x94 and xe2x80x94[B]T
wherein A is monomer repeat unit derived from one or more norbornene or substituted norbornene monomers of the formula: 
and B is a monomer repeat unit derived from one or more functional norbornene monomers selected from Set 1;
Set 1 
wherein,
R7a-b are independently selected from H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl;
R8a-b are independently selected from H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, or xe2x80x94C(O)xe2x80x94R9 where R9 is hydrocarbyl or substituted hydrocarbyl;
R5a-b and R6a-b are each independently H, hydrocarbyl, halogen, halohydrocarbyl, or
R5a-b and R6a-b may be taken together to form a ring, and S and T represent the mole fraction of the respective monomer unit and sum to one with the proviso that T greater than 0.
These polymers can be prepared by the transition metal catalyzed polymerization of norbornene and functional norbornene comonomers. Therefore, the polymers of the invention described herein are derived from the addition copolymerization of A and B type monomers. As an example, the polymerization of norbornene and B2 would give a random compolymer having the following monomer repeat units. 
Therefore, the phrase xe2x80x9ca monomer repeat unit derived from one or more norbornene, substituted norbornene or functional norbornene monomersxe2x80x9d refers to the product of the transition metal catalyzed addition polymerization of said monomers as depicted in the above example. Although it is understood that this example only depicts one combination of A and B type monomers, many other combinations are possible.
In a preferred embodiment, the polymer composition is terminated with an olefinic moiety from a chain transfer agent wherein said agent is a compound having a terminal olefinic double bond between adjacent carbon atoms, provided that said agent is other than a compound selected from the classes of styrenes, vinyl ethers and conjugated dienes, and wherein at least one of said adjacent carbon atoms has two hydrogen atoms attached thereto, and wherein the moiety derived from said chain transfer agent is exclusively located at the terminal end of said polymer. Said chain transfer agent is used to control the molecular weight of these cyclic olefin copolymers. It is often the case that due to the high relative propagation rates to chain transfer rates that in the absence of a chain transfer agent very high molecular weights for these cyclic olefin polymers are obtained. Introduction of a chain transfer agent allows for the predictable control of molecular weight. In a further preferred embodiment, the chain transfer agent is a compound of the following formula: 
wherein R10a-b are independently selected from a hydrogen atom, hydrocarbyl, and substituted hydrocarbyl. In addition, H2 can be used as a chain transfer agent. As noted above, these are useful in dielectric, optical, and photolithographic applications. In addition, the utility of these materials as engineering thermoplastics has been explored.
In another embodiment of this invention, certain nickel catalysts have been shown to be effective catalysts for the preparation of norbornene functional norbornene copolymers. Thus, as a further aspect of the invention, there is provided a process for preparing a polymer composition comprising repeat units of the formula:
xe2x80x83[A]Sxe2x80x94 and xe2x80x94[B]T
which comprises contacting norbornene or a substituted norbornene of formula I 
with one or more functional norbornenes monomers selected from 
wherein,
R7a-b is independently selected from H, hydrocarbyl, subsituted hydrocarbyl, fluoroalkyl;
R8a-b is independently selected from H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, C(O)xe2x80x94R9 where R9 is hydrocarbyl or substituted hydrocarbyl;
R5a-b and R6a-z are each independently selected from H, hydrocarbyl, halogen, halohydrocarbyl, R5a-b and R6a-b may be taken together to form a ring, and S and T represent the mole fraction of the respective monomer unit and sum to one with the proviso that T greater than 0,
in the presence of a transition metal complex of formula II: 
wherein:
M is nickel;
D1, D2, and G collectively comprise therefor a monoanionic bidentate ligand;
D1 and D2 are monodentate donors linked by a bridging group G, wherein at least one of D1 and D2 is ligated to the metal M by a nitrogen atom substituted by a 1-pyrrolyl or a substituted. 1-pyrrolyl group;
T is H, hydrocarbyl, substituted hydrocarbyl, or other group capable of inserting an olefin; and
L is an olefin or a neutral donor group capable of being displaced by an olefin; in addition, T and L may be taken together to form a xcfx80-allyl or xcfx80-benzyl group or other bidentate group.
Examples of preferred monoanionic bidentate donors are shown in Set 2:
Set 2 
wherein:
R2a-z are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl; R2a-w may also be silyl, boryl, or ferrocenyl; in addition, any two of R2a-w, or R2x and R2y, may be linked by a bridging group;
R3a-z are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two of R3a-z may be linked by a bridging group;
R4a and R4b are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl; in addition, R4a and R4b may be linked by a bridging group;
E2 and E3 are O, S, or NR2a; and
Q is Cxe2x80x94R3a, PR4aR4b, S(E2)(NR2aR2b) or S(E2)(E3R2a).
The present invention further comprises, a process for preparing a polymer composition comprising repeat units of the formula:
[A]Sxe2x80x94 and xe2x80x94[B]T
which comprises contacting norbornene or a subsituted norbornene of formula I 
with one or more functional norbornene monomers selected from 
wherein,
R7a-b is independently selected from H, hydrocarbyl, subsituted hydrocarbyl, fluoroalkyl;
R8a-b is independently selected from H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, C(O)xe2x80x94R9 where R9 is hydrocarbyl or substituted hydrocarbyl;
R5a-b and R6a-z are each independently selected from H, hydrocarbyl, halogen, halohydrocarbyl, R5a-b and R6a-b may be taken together to form a ring, and S and T represent the mole fraction of the respective monomer unit and sum to one with the proviso that T greater than 0, with the reaction product of Ni(COD)2 and tris(pentafluorophenyl)borane.
The present invention further comprises a process for preparing a polymer composition comprising repeat units of the formula:
[A]Sxe2x80x94 and xe2x80x94[B]T
which comprises contacting norbornene or a subsituted norbornene of formula I 
with one or more functional norbornene monomers selected from 
wherein,
R7a-b is independently selected from H, hydrocarbyl, subsituted hydrocarbyl, fluoroalkyl;
R8a-b is independently selected from H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, C(O)xe2x80x94R9 where R9 is hydrocarbyl or substituted hydrocarbyl;
R5a-b and R6a-z are each independently selected from H, hydrocarbyl, halogen, halohydrocarbyl, R5a-b and R6a-b may be taken together to form a ring, and S and T represent the mole fraction of the respective monomer unit and sum to one with the proviso that T greater than 0, with the reaction product of a ligand from Set 3, Ni(COD)2 and tris(pentafluorophenyl)borane.
Set 3 
In this disclosure, symbols ordinarily used to denote elements in the Periodic Table take their ordinary meaning, unless otherwise specified. Thus, N, O, S, P, and Si stand for nitrogen, oxygen, sulfur, phosphorus, and silicon, respectively.
A xe2x80x9cxe2x80x94NR2aR2bxe2x80x9d group refers to a group of formula Ia below: 
wherein R2a and R2b are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, silyl, boryl, or ferrocenyl; in addition, R2a and R2b may be connected to form a ring.
A xe2x80x9c1-pyrrolyl or substituted 1-pyrrolylxe2x80x9d group refers to a group of formula III below: 
wherein R3a-d are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two or more of R3a-d may be linked by a bridging group or groups.
A xe2x80x9chydrocarbylxe2x80x9d group means a monovalent or divalent, linear, branched or cyclic group which contains only carbon and hydrogen atoms. Examples of monovalent hydrocarbyls include the following: C1-C20 alkyl; C1-C20 alkyl substituted with one or more groups selected from C1-C20 alkyl, C3-C8 cycloalkyl, and aryl; C3-C8 cycloalkyl; C3-C8 cycloalkyl substituted with one or more groups selected from C1-C20 alkyl, C3-C8 cycloalkyl, and aryl; C6-C14 aryl; and C6-C14 aryl substituted with one or more groups selected from C1-C20 alkyl, C3-C8 cycloalkyl, and aryl; where the term xe2x80x9carylxe2x80x9d preferably denotes a phenyl, napthyl, or anthracenyl group. Examples of divalent (bridging) hydrocarbyls include: xe2x80x94CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94, and 1,2-phenylene.
A xe2x80x9csilylxe2x80x9d group refers to a SiR3 group wherein Si is silicon and R is hydrocarbyl or substituted hydrocarbyl or silyl, as in Si(SiR3)3.
A xe2x80x9cborylxe2x80x9d group refers to a BR2 or B(OR)2 group, wherein R is hydrocarbyl or substituted hydrocarbyl.
A xe2x80x9cheteroatomxe2x80x9d refers to an atom other than carbon or hydrogen. Preferred heteroatoms include oxygen, nitrogen, phosphorus, sulfur, selenium, arsenic, chlorine, bromine, silicon, and fluorine.
A xe2x80x9csubstituted hydrocarbyixe2x80x9d refers to a monovalent, divalent, or trivalent hydrocarbyl substituted with one or more heteroatoms. Examples of monovalent substituted hydrocarbyls include: 2,6-dimethyl-4-methoxyphenyl, 2,6-diisopropyl-4-methoxyphenyl, 4-cyano-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl, 2,6-difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 4-methoxycarbonyl-2,6-dimethylphenyl, 2-tert-butyl-6-chlorophenyl, 2,6-dimethyl-4-phenylsulfonylphenyl, 2,6-dimethyl4-trifluoromethylphenyl, 2,6-dimethyl-4-trimethylammoniumphenyl (associated with a weakly coordinated anion), 2,6-dimethyl-4-hydroxyphenyl ,9-hydroxyanthr-10-yl, 2-chloronapth-1-yl, 4-methoxyphenyl, 4-nitrophenyl, 9-nitroanthr-10-yl, -CH2OCH3, cyano, trifluoromethyl, and fluoroalkyl. Examples of divalent (bridging) substituted hydrocarbyls include: 4-methoxy-1,2-phenylene, 1-methoxymethyl-1,2-ethanediyl, 1,2-bis(benzyloxymethyl)-1,2-ethanediyl, and 1-(4-methoxyphenyl)-1,2-ethanediyl.
A xe2x80x9cheteroatom connected hydrocarbylxe2x80x9d refers to a group of the type E10(hydrocarbyl), E20H(hydrocarbyl), or E20(hydrocarbyl)2, where E10 is an atom selected from Group 16 and E20 is an atom selected from Group 15.
A xe2x80x9cheteroatom connected substituted hydrocarbylxe2x80x9d refers to a group of the type E10(substituted hydrocarbyl), E20H(substituted hydrocarbyl), or E20(substituted hydrocarbyl)2, where E10 is an atom selected from Group 16 and E20 is an atom selected from Group 15.
The term xe2x80x9cfluoroalkylxe2x80x9d as used herein refers to a C1-C20 alkyl group substituted by one or more fluorine atoms.
In some cases, the Group 8-10 catalysts can be inhibited by olefins that contain additional olefinic or acetylenic functionality. This is especially likely if the catalyst is prone to xe2x80x9cchain-runningxe2x80x9d wherein the catalyst can migrate up and down the polymer chain between insertions, since this can lead to the formation of relatively unreactive xcfx80-allylic intermediates when the olefin monomer contains additional unsaturation.
The term xe2x80x9cxcex1-olefinxe2x80x9d as used herein is a 1-alkene with from 3 to 40 carbon atoms.
A xe2x80x9cxcfx80-allylxe2x80x9d group refers to a monoanionic group with three sp2 carbon atoms bound to a metal center in a xcex73-fashion. Any of the three sp2 carbon atoms may be substituted with a hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or O-silyl group. Examples of xcfx80-allyl groups include: 
The term xcfx80-benzyl group denotes an xcfx80-allyl group where two of the sp2 carbon atoms are part of an aromatic ring. Examples of xcfx80-benzyl groups include: 
xe2x80x9cBridging groupxe2x80x9d refers to an atom or group which links two or more groups, which has an appropriate valency to satisfy its requirements as a bridging group, and which is compatible with the desired catalysis. Suitable examples include divalent or trivalent hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, substituted silicon(IV), boron(III), N(III), P(III), and P(V), xe2x80x94C(O)xe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94C(S)xe2x80x94, xe2x80x94B(OMe)xe2x80x94, xe2x80x94C(O)C(O)xe2x80x94, O, S, and Se. In some cases, the groups which are said to be xe2x80x9clinked by a bridging groupxe2x80x9d are directly bonded to one another, in which case the term xe2x80x9cbridging groupxe2x80x9d is meant to refer to that bond. By xe2x80x9ccompatible with the desired catalysis,xe2x80x9d we mean the bridging group either does not interfere with the desired catalysis, or acts to usefully modify the catalyst activity or selectivity.
The catalysts of the present invention may be used in batch and continuous processes, in solution or slurry or gas phase processes.
In some cases, it is advantageous to attach the catalyst to a solid support. Examples of useful solid supports include: inorganic oxides, such as talcs, silicas, titania, silica/chromia, silica/chromia/titania, silica/alumina, zirconia, aluminum phosphate gels, silanized silica, silica hydrogels, silica xerogels, silica aerogels, montmorillonite clay and silica co-gels, as well as organic support materials such as polystyrene and functionalized polystyrene. (See, for example, S. B. Roscoe et al., xe2x80x9cPolyolefin Spheres from Metallocenes Supported on Non-interacting Polystyrene,xe2x80x9d 1998, Science, 280, 270-273 (1998)).
The monomeric species of Set 1 above can be easily prepared by the Diels-Alder cycloaddition of a diene with a dienophile. This reaction is represented by the following general reaction scheme, in which the diene D is reacted at elevated temperature with the dienophile E giving the monomer of the general formula I: 
A specific example of such a reaction is the reaction of cyclopentadiene with 3,4-epoxybutene (reacted for 66 hours at 170xc2x0 C.). 
The ligands of the present invention may be prepared by methods known to those skilled in the art, wherein a substituted 1 -aminopyrrole is condensed with a mono-aldehyde, mono-ketone, di-aldehyde or di-ketone to afford the desired ligands (Scheme II). The requisite substituted 1-aminopyrroles may be prepared by any of a variety of methods, including those shown in Scheme III. 
Other features of the invention will become apparent in the following description of working examples, which have been provided for illustration of the invention and are not intended to be limiting thereof.